Int. J. Environ. Sci. Technol.
DOI 10.1007/s13762-017-1253-y
ORIGINAL PAPER
Effect of Fenton process on treatment of simulated textile
wastewater: optimization using response surface methodology
S. Sharma1 • S. Kapoor2 • R. A. Christian3
Received: 28 January 2016 / Revised: 12 August 2016 / Accepted: 30 January 2017
Ó Islamic Azad University (IAU) 2017
Abstract A large portion of water is consumed during
various textile operations thereby discharging wastewaters
with pollutants of huge environmental concern. The treat-
ment of such wastewaters has promising impact in the field
of environmental engineering. In this work, Fenton oxi-
dation treatment was engaged to treat simulated textile
wastewater. Box–Behnken design and response surface
methodology were employed to optimize the efficiency of
Fenton process. Iron dose, peroxide dose and pH were
considered as input variables while the responses were
taken as chemical oxygen demand and color removal. A
total of 17 experiments were conducted and analyzed using
second-order quadratic model. The quadratic models gen-
erated for chemical oxygen demand and color removal
efficiencies were validated using analysis of variances, and
it was found that the experimental data fitted the second-
order model quite effectively. Analysis of variances
demonstrated high values of coefficient of determination
(R2) for chemical oxygen demand and color removal effi-
ciencies with values of 0.9904 and 0.9963 showing high
Editorial responsibility: M. Abbaspour.
Electronic supplementary material The online version of this
article (doi:10.1007/s13762-017-1253-y) contains supplementary
material, which is available to authorized users.
& S. Kapoor
shivamkpr88@gmail.com
1
Civil Engineering Department, CSPIT, CHARUSAT,
Changa, Gujarat, India
2
Indian Institute of Technology, Bombay, Maharashtra, India
3
SV National Institute of Technology, Surat, Gujarat, India
conformation of predicted values to the experimental ones.
Perturbation plots suggested that the iron dosage produced
the maximum effect on both chemical oxygen demand and
color removal efficiencies. The optimum parameters were
determined as Fe2? dose—550 mg/L, H2O2 dose—
5538 mg/L, pH—3.3 with corresponding chemical oxygen
demand and color removal efficiencies of 73.86 and
81.35%. Fenton process was found efficient in treatment of
simulated textile wastewater, and optimization using
response surface methodology was found satisfactory as
well as relevant. From the present study, it can also be
concluded that if this method is used as pretreatment
integrated with biological treatment, it can lead to eco-
friendly solution for treatment of textile wastewaters.
Keywords Analysis of variances  Box–Behnken design 
Color removal  Chemical oxygen demand  Azo dye
Introduction
The accelerated development of textile industries is
enhancing higher rate of water pollution in the environment
(Nidheesh et al. 2013). Dye molecules consist of two key
segments: chromophores, helps in producing color and
auxochromes which are accountable for enhancing affinity
toward the fiber and render the molecule soluble in water
(Nidheesh et al. 2013). The most significant chromophores
are azo (–N=N–), carbonyl (–C=O), methine (–CH=), nitro
(–NO2) and quinoid groups. The most important aux-
ochromes are amine (–NH3), carboxyl (–COOH), sulfonate
(–SO3H) and hydroxyl (–OH) (Dos Santos et al. 2007). The
auxochromes can be owned to the classes of reactive, acid,
direct, basic, mordant, disperse, pigment, vat, ingrain,
sulfur and solvent dye (Welham 2000).
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Enormous quantities of wastewater with significant
concentrations of chemical oxygen demand (COD), sus-
pended solids, refractory organics and color are introduced
to the environment by textile industries (Garca-Montano
et al. 2006). Discharge of textile processed effluents has
created unfavorable conditions in the environment (Emami
et al. 2010) like reduction in solar energy penetration to the
aquatic bodies, reduced reoxygenation capacity and being
highly toxic toward aquatic flora and fauna (Clarke and
Anliker 1980). Additionally, they are resilient to degrada-
tion due to their complex chemical structure and xenobiotic
properties (Cristovao et al. 2011).
Azo dyes consist of –N=N– bond and are the most
commonly used dyes (Meric et al. 2004). Degradation of
azo dyes which contributes about 70% of all used dyes is
crucial due to their high structural diversity (Nidheesh et al.
2013). Moreover, the reductive cleavage of azo bonds is
responsible for the formation of metabolites of amines,
which are classified as toxic and carcinogenic (Pu-
vaneswari et al. 2006) and more noxious than intact dye
molecules (Chung et al. 1978). Viewing the inimical
effects on environment due to dyes, it becomes necessary
to have an adequate treatment for textile wastewaters.
There are numerous physicochemical techniques used
like adsorption by activated carbon (Nawaz and Ahsan
2014), photocatalysis and photocatalytic oxidation (Alin-
safi et al. 2007), chemical coagulation (Yadav et al.
2013), ozonation (Sevimli and Sarikaya 2002) and
chemical precipitation (Tunay et al. 1996) which have
been reviewed for treatment of textile wastewater and
their COD and color removal efficiencies are given in
Table 1. However, physical and chemical treatment
techniques are powerful in color removal but allow only a
phase transfer of pollutant requiring additional treatment
or disposal (Blanco et al. 2012). Moreover, most of the
organic matter present in textile wastewater is non-
biodegradable or toxic, and therefore, it becomes difficult
for biological treatment to reach its required efficiency
(Ugyur and Kök 1999).
Table 1 COD and color removal efficiencies of different physicochemical techniques
Sr. nos. Method used COD removal (%)
1 Adsorption by granular activated carbon 56
2 Chemical coagulation (using FeCl3) 47.6
3 Ozonation 10–20
4 Photocatalysis 32
5 Photocatalytic oxidation 28
6 Chemical precipitation 22
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Int. J. Environ. Sci. Technol.
In this frame, advanced oxidation processes (AOPs) are
the ones involving the production of hydroxyl radical (OH,
E° = 2.8 V vs. NHE), efficient enough to destroy the
recalcitrant compounds to CO2 and H2O (Blanco et al.
2012; Mansoorian et al. 2014). Among AOPs, Fenton
oxidation has come out as a promising treatment technique
for textile wastewaters (Nidheesh et al. 2013). Fenton
reagent is a homogenous catalytic oxidation process that
uses a mixture of ferrous ion and hydrogen peroxide in an
acidic medium for generation of hydroxyl radicals (Bah-
mani et al. 2013). Chain reactions involved in Fenton
oxidation process are shown below in Eqs. 1 and 2 (Bianco
et al. 2011):
Fe2þ þ H2 O2 ! Fe3þ þ HO þ HO  ðchain initiationÞ
ð1Þ
2þ 3þ 
OH  þFe ! Fe þ HO ðchain terminationÞ ð2Þ
The advantages of Fenton reagent are high efficiency,
easy applicability, low investment cost (Rodrigues et al.
2009), lack of residues, capacity to treat complex
compounds (Bianco et al. 2011) and less environmental
damages (Babuponnusami and Muthukumar 2014),
whereas the limitations of this process are production of
sludge containing high amounts of ferric ions as well as
higher operational costs due to usage of chemical reagents
(Meric et al. 2004; Sun et al. 2007).
The process parameters are required to determine the
performance of Fenton reaction (Zhu et al. 2011).
Response surface methodology (RSM) is a useful statistical
method widely used for experimental design and widely
applied for optimization of wastewater treatment (Rosales
et al. 2012). Rare studies for optimization of simulated
textile wastewater with a mixture of 5 azo dyes with Fenton
process have been performed. The most relevant part of
RSM is the selection of applicable design of experiment
that has higher impact on response surface and its accuracy
on prediction (Sakkas et al. 2010). The application of Box–
Behnken design (BBD) is a standard, stable and favored
Color removal (%) References
88 Nawaz and Ahsan (2014)
75 Yadav et al. (2013)
75 Sevimli and Sarikaya (2002)
51 Alinsafi et al. (2007)
42 Alinsafi et al. (2007)
55 Tunay et al. (1996)
Int. J. Environ. Sci. Technol.

Table 2 Constituents of Sr. nos. Materials used Concentration (mg/L) Functions of material
simulated textile
wastewater.Isik and Sponza 1 Carboxymethyl cellulose 150 Sizing in reactor
(2008)
2 Starch 1500 Sizing in reactor
3 Acetic Acid 500 Substrate in reactor
4 Azo dyes Dying in reactor
Direct red 80 50
Reactive black 5 50
Direct black 38 50
Direct blue 71 50
Direct fast yellow 5GL 50
5 NaOH 660 Hydrolysis
6 H2SO4 357 pH neutralization
7 NaCl 500 Fixing
8 Na2CO3 1000 Fixing
9 NaHCO3 2000 pH buffer
10 Glucose 2000 Substrate for bacterial growth
11 NH4Cl 280 Nutrient for bacterial growth
12 K2HPO4 250 Nutrient for bacterial growth
13 MgSO47H2O 100 Nutrient for bacterial growth
14 CaCl22H2O 10 Nutrient for bacterial growth

design used for examining the interaction between vari-
ables. BBD is usually very competent due to reduced
number of experiments (Nair et al. 2014) and due to
inconsideration of points at the vertices of a cube which
could be considered as an advantage as experiments carried
out at these points may turn out to be either expensive or
unfeasible (Montogomery 2010). As BBD designs are
economical, they are widely used for research purposes.
In this study, Box–Behnken design and response surface
methodology were applied to design the experiments and
assess the effects of variables like pH, iron and hydrogen
peroxide concentration on application of Fenton oxidation
treatment to simulated textile wastewater. Two regression
models were developed with the experimental data, i.e.,
one for COD removal and one for color removal. The
significance of each variable on the efficiency of Fenton
process was studied, and optimal values were acquired and
ratified. This study was carried out at Sardar Vallabhbhai
National Institute of Technology, Surat, Gujarat, India
during August 2014–April 2015.
industry. The simulated textile wastewater was prepared in
agreement with the information presented in Table 2, and
the characteristics obtained are shown in Table 3.
Samples of the auxiliary products and dyes as presented
in Table 2 were taken from Isik and Sponza 2008. The
mixture of azo dyes was prepared with concentration
50 mg/L each of Reactive Black 5, Direct Red 80, Direct
Black 38, Direct Blue 71 and Direct Fast Yellow 5GL.
Chemicals
All chemicals used in the study were of highest commer-
cially available grade. Analytical grade hydrogen peroxide
(30% (w/v), Finar Limited, India) and FeSO47H2O
(RFCL, India) were used to generate hydroxyl radical in
aqueous solution. pH adjustment was done using reagent
grade sulfuric acid and sodium hydroxide (RFCL, India)
solutions. All the solutions were prepared in distilled water.

Materials and methods

Table 3 Characteristics of simulated textile wastewater
Simulated textile wastewater Sr. nos. Parameter Values

1 pH 8.25 ± 2.5
In this study, simulated textile wastewater was used as the
2 COD (mg/L) 3894 ± 100
composition of real textile wastewater changes day to day
3 Absorbance at 478 nm 0.9417 ± 0.014
owing to different operations taking place in textile

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Fenton oxidation
Batch experiments of Fenton oxidation were carried out in
glass beakers having 1 liter of operating capacity at room
temperature (25–30 °C). pH of the sample was adjusted in
the range of 2.5–3.5 using 0.5 M H2SO4. After adjusting
pH, catalyst FeSO47H2O was added and reaction pro-
ceeded with further addition of H2O2 producing hydroxyl
radicals. During the reaction, sample solution was con-
stantly stirred using magnetic stirrer at 150 rpm for 60 min.
After 60 min, residual hydrogen peroxide was eliminated
by addition of excess sodium sulfite (Finar Limited, India)
and by adjusting pH [ 7 before analysis. Settling of sam-
ples was carried out in Imhoff cone for 2 h, and samples
were analyzed thereafter.
Analytical procedures
The color of the samples was analyzed by measuring the
absorbance of supernatant sample at wavelength corre-
sponding to the maximum absorbance, i.e., 478 nm in UV–
Vis Spectrophotometer (Hach DR 6000TM). As the sample
absorbance varied with pH, it was adjusted similar for all
supernatant samples. Analytical methods carried out for
remaining parameters followed standard methods. COD of the
samples was measured using Open Reflux Method (Method
5220 B). pH of the sample was determined using pH-meter.
Dye decolorization and COD removal were calculated
using expressions (3) and (4):
R1 ð%Þ ¼ 100  ðAi  At Þ=Ai ð3Þ
R2 ð%Þ ¼ 100  ðCi Ct Þ=Ci ð4Þ
where R1—decolorization efficiency (%), R2—COD
removal efficiency (%); Ai and At, initial and final absor-
bance at maximum wavelength; Ci and Ct, initial and final
COD (mg/L) of simulated textile wastewater.
Experimental design, analysis and statistical
validation
Response surface methodology (RSM) was used for the
optimization of experiments. RSM is an extensively used
statistical tool applied in engineering process (Xu et al.
2013). Whenever multiple variables and their interactions
affect the responses, RSM can be applied to examine the
relation between independent and dependent variables
along with optimization of parameters (Baş and Boyaci
2007). Under RSM, for a selected response, it is possible to
restrict the number of experiments for recognition of
optimal conditions (Rosales et al. 2012). Optimization by
RSM involves following steps: (1) selection of independent
variables and their ranges, (2) experimental design
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Int. J. Environ. Sci. Technol.
selection, (3) estimation of mathematical coefficients using
linear regression analysis technique and (4) verification of
model adequacy and obtaining optimal conditions (Nair
et al. 2014). Optimization of results is faster by using RSM
rather than one factor at a time approach (Alim et al. 2008).
In this study, Box–Behnken design (BBD) which is
widely used in RSM was employed for optimization of
COD and color removal efficiencies in simulated textile
wastewater. Here, a 23 factorial design was used to per-
ceive the influence of 3 parameters including: H2O2 con-
centration (A), Fe2? concentration (B) and pH (C). These
factors were chosen as they might show some promising
effect on COD and color removal efficiencies. A total of 17
experiments were conducted with 5 replicates at the central
point, and the codification of values was done using Eq. 5:
xi ¼ zi zo =Dzi ð5Þ
where xi = code level, zi = uncoded value, zo corresponds
to the uncoded value at the central point and Dzi = step
change value between low level (-1) and high level (?1)
(Moghaddam et al. 2010). From preliminary experiments,
the range of A, B and C was selected as shown in Table 4.
A second-order regression model was employed for
analysis and proves to be a good estimation of response
surface (Zhu et al. 2011) and is expressed as shown in Eq. 6:
X
k X
k k¼1 X
X k
y ¼ b0 þ b i Xi þ bii Xi2 þ bij Xi Xj ð6Þ
i¼1 i¼1 i¼1 j¼iþ1
where y = response; xi and xj = input variables; b0 = in-
tercept constant; bi = first-order regression coefficient;
bii = second-order regression coefficient representing
quadratic effect of factor i; and bij = coefficient of inter-
action between two factors i and j (Xu et al. 2013).
The analysis of variances (ANOVA) was carried out
using Design Expert (version 9.0.0) to study the results
and to determine the implication of fitted quadratic
model. The fitted model was thereafter illuminated in the
form of contour and surface plots to know the interaction
between the variables and responses. The quality of
model was checked using co-relation coefficient (R2)
(GilPavas et al. 2012). The model was further authenti-
cated with respect to all the three variables within the
design space.
Table 4 Coded level and independent variables used in BBD
Coded level Fe?2 dose (mg/L) H2O2 dose (mg/L) PH
-1 450 4400 2.5
0 600 6600 3
1 750 8800 3.5
Int. J. Environ. Sci. Technol.

Results and discussion
Preliminary experiments
In this work, before optimization preliminary experiments
were carried out to know the range in which maximum
color and COD removal took place. The range obtained for
Fe2? concentration was 450–750 mg/L, hydrogen peroxide
range was 4400–8800 mg/L, pH was varied from 2.5 to 3.5
as maximum removal of COD, and color was obtained in
these ranges. Further precision of doses was done with the
help of RSM.
Experimental design by BBD under RSM
According to 23 BBD factorial design experiments were
designed and carried out. Among 17 experiments, five
experiments were repetition of central point (Run 2, 11, 14,
15 and 16). These runs enclosed the variables which were
at central region of the cube. Proximity of the results for
these runs shows the symbol of precision maintained dur-
ing the experimentation work (Azami et al. 2012). The
results obtained from experimental design are shown in
Table 5.
Regression model and statistical testing
For determination of optimal values for decolorization
and COD removal within the experimental runs, a second-
order polynomial fitted for the results of color and COD
removal. The polynomials obtained are shown in Eqs. 7
and 8:
R1 ¼ 82:22  3:81A þ 2:46B þ 2:07C
ð7Þ
24:64A2  8:79B2  10:45C2
R2 ¼ 88:26  6:80A þ 2:76B  3:40AB  29:54A2
 6:37B2  7:12C2 ð8Þ
where R1 and R2 accounts for COD and color removal,
respectively. Tables 6 and 7 shows the ANOVA report
generated for this model. In Eqs. 7 and 8, positive effect of
a factor means that the response is improved when the
factor level increases and a negative effect of the factor
means that the response is not improved when the factor
level increases (Saldańa-Robles et al. 2014). Values of
probability \ 0.05 indicate that model terms are significant
and values [ 0.1000 indicate that model terms are not
significant (Rosales et al. 2012). In the case of COD
removal, it can be seen that A, B, C, A2, B2 and C2 were
significant terms, and rest of the terms were not significant
and therefore, not included in the equation for COD
removal while for color removal, it was concluded that A,
B, AB, A2, B2 and C2 proved to be significant. Thus, sta-
tistical analysis showed that not all variables set in the
grounding of model within the tested limitations and had
noteworthy effect.
The impact of each factor and interactions between each
other is checked by Fisher test. The better the magnitude of
F value and likewise the lesser the ‘p [ F’, the more

Table 5 Box–Behnken design Run A (mg/L) B (mg/L) C R1 COD removal (%) R2 Color removal (%)
matrix along with experimental
and predicted values Experimental Predicted Experimental Predicted

1 0 -1 -1 62.1 60.51 70.4 70.60

2 0 0 0 81.6 82.22 87.9 88.26
3 -1 1 0 59.4 56.98 64.7 65.31
4 1 1 0 46 45.55 45.9 44.91
5 0 -1 1 61.8 60.51 74 73.42
6 0 1 -1 60 61.29 75.8 76.38
7 -1 0 1 54.9 55.74 60 59.59
8 1 -1 0 42 44.42 46.8 46.19
9 -1 -1 0 47.8 48.25 52 52.99
10 -1 0 -1 45 46.14 58.4 57.21
11 0 0 0 83.6 82.22 89.4 88.26
12 1 0 -1 44.8 43.96 43 43.41
13 0 1 1 68 69.59 78.9 78.70
14 0 0 0 84.6 82.22 89.8 88.26
15 0 0 0 80.3 82.22 85.6 88.26
16 0 0 0 81 82.22 88.6 88.26
17 1 0 1 43.8 42.66 45 46.19

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 Int. J. Environ. Sci. Technol.

Table 6 ANOVA for response Source Sum of squares Degree of freedom Mean square F value p value Prob [ F
surface second-order model for
COD removal Model 3887.53 9 431.95 80.33 \0.0001
A 116.28 1 116.28 21.62 0.0023
B 48.51 1 48.51 9.02 0.0198
C 34.45 1 34.45 6.41 0.0392
AB 14.44 1 14.44 2.69 0.1453
AC 29.70 1 29.70 5.52 0.0511
BC 17.22 1 17.22 3.20 0.1166
A2 2555.30 1 2555.30 475.21 \0.0001
B2 324.95 1 324.95 60.43 0.0001
C2 460.68 1 460.68 85.67 \0.0001
Residual 37.64 7 5.38 – –
Std. dev – 2.32 – – –
Mean – 61.57 – – –
C.V (%) – 3.77 – – –
R2 – – – – 0.9904
Adjusted R2 – – – – 0.9781
Predicted R2 – – – – 0.8949
Adeq. precisior – – – – 22.242

Table 7 ANOVA for response Source Sum of squares Degree of freedom Mean square F value p value Prob [ F
surface second-order model for
color removal Model 4782.04 9 531.34 211.39 \0.0001
A 369.92 1 369.92 147.17 \0.0001
B 61.05 1 61.05 24.29 0.0017
C 13.26 1 13.26 5.26 0.0552
AB 46.24 1 46.24 18.40 0.0036
AC 0.040 1 0.040 0.016 0.9032
BC 0.063 1 0.063 0.025 0.8792
A2 3674.78 1 3674.78 1462.02 \0.0001
B2 170.72 1 170.72 67.92 \0.0001
C2 213.30 1 213.30 84.86 \0.0001
Residual 17.59 7 2.51 – –
Std. dev – 1.59 – – –
Mean – 68.01 – – –
C.V (%) – 2.33 – – –
R2 – – – – 0.9963
2
Adjusted R – – – – 0.9916
Predicted R2 – – – – 0.9744
Adeq. Precisior – – – – 36.863

considerable are equivalent model and individual coeffi-
cients (Montogomery 2010). From ANOVA, it was
observed that the corresponding F values for COD and
color removal efficiencies were 80.39 and 211.39 with a
very low probability value (p value \ 0.0001) which
indicated there was only 0.01% chance that such model
could occur due to noise. The F values for COD and color
removal indicate that both models were extremely signifi-
cant and adequate as they were much larger than the crit-
ical F value of 2.42 (Rosales et al. 2012).
The overall performance of a model is generally
explained by coefficient of determination (R2) (Nair et al.

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Int. J. Environ. Sci. Technol.
2014). For a model to be highly competent, the value of R2
should be nearest to 1.0. The R2 evaluates the correlation
between experimental data and predicted responses (Fathinia
et al. 2010). R2 values for COD and color removal were
obtained as 0.9904 and 0.9963 which indicated that the
predicted values matched the experimental ones quite real-
istically. The models of COD and color removal indicated
that 99.04 and 99.63% of the total variability could be
explained by these models leaving 0.96 and 0.37% of vari-
ability owing to random error. Figure 1 suggests that the
predicted values conformed well to the experimental values
of COD and color removal of simulated textile wastewater.
The model prediction competency should not be examined
by R2 value alone (Sarabia and Ortiz 2009) as R2 value
increases with the increase in number of terms in model,
irrespective of its statistical significance. R2 should be
related to adjusted R2 which reflects the number of factors in
experiment (Montogomery 2010). The predicted value of R2
and the adjusted value of R2 were in reasonable agreement
for both COD and color removal because the difference
between both the values was \ 0.2. The value of predicted
R2 for COD and color removal was 0.8949 and 0.9744,
while the adjusted R2 values were 0.9781 and 0.9916. As the
difference between predicted and adjusted R2 was less for
both models, adequacy of model seemed to be eminently
convincing with high values of adjusted R2 confirming
model of strong implication.
Another statistical tool observed for model adequacy is
adequate precision. It scrutinizes the range of the predicted
values at the design points to the average prediction error,
in other words a signal-to-noise ratio (Mason et al. 2003).
Fig. 1 Predicted versus actual plot for a COD removal, b Color removal
The values of adequate precision are in range with a pre-
cision of 22.242 for COD removal and 36.883 for color
removal. The obtained ratio indicates an adequate signal as
values [ 4 are desirable. Thus, this model can be used to
navigate the design space.
The coefficient of variation is defined as the ratio of
standard deviation to the mean value of observed response.
This factor demonstrates the repeatability and repro-
ducibility of the models generated (Rosales et al. 2012).
Low values of C.V, i.e., 3.77 and 2.33 for COD and color
removal indicated high accuracy and dependability of
experiments as the values are \10%.
The sufficiency of the models was also evaluated by the
residuals (difference between the observed and the pre-
dicted responses). Residuals act as components of variation
unidentified by the fitted model, and so, they should have a
normal distribution (Khataee et al. 2012). Normal proba-
bility plots are formed in order to check normality pre-
sumption (Nair et al. 2014). If the plots are normally
distributed, the residual plots will maintain linearity with
some moderate irregularity of points showing appropriate
fitting of model (Carlson and Carlson 2005; Anderson and
Whitcomb 2007). The points should distribute uniformly
along 45° line maintaining linearity, whereas the points
above and under the line indicate areas of over or under
prediction (Anderson and Whitcomb 2007). Thus, a review
was made for COD and color removal of simulated textile
wastewater using normalized plot of residuals as seen in
Fig. 2 which showed satisfying normality assumption as
the points for both COD and color maintained linearity
with the values.
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(a) Normal Plot of Residuals
99
95
Normal % Probability
90
80
70
50
30
20
10
5 5
1 1
-3 -2 -1 0 1
Residuals
Fig. 2 Normal probability plots of studentized residual of the linear model for a COD removal, b Color removal
Chemical oxidation by Fenton
Response surface and contour plots for simulated textile
wastewater treatment
The response surface (3D) and contour plots (2D) of the
model-predicted responses obtained from Design Expert
software (version 9.0.0) supported in determining the
interactive relationships between the process variables and
treatment outputs.
Effect of Fe2? concentrations on COD and color removal
efficiency
Figure 3 exhibits the 3D and 2D plots for the effect of iron
concentration on COD removal. As it can be seen from
response surface and contour plots, the peak values for both
the plots were attained at the values in middle ranges of
iron. The values of COD removal increased from 50.5 to
71% for iron doses of 450–600 mg/L and then decreased
from 67.8 to 46.4% for iron doses of 650–750 mg/L at
hydrogen peroxide dose of 4400 mg/L. Removal of COD
can be attributed to the fact that at higher concentration of
iron, decomposition of hydrogen peroxide is accelerated
leading to the formation of per-hydroxyl radicals (HO2)
(Mansoorian et al. 2014), while at lower iron concentration,
the reaction with hydrogen peroxide leads to the formation
of hydroxyl radicals which are more reactive than per-hy-
droxyl radicals. It was reported that methylene red removal
was increased from 45 to 75% in the presence of iron ions
(Zhou et al. 2007). Wang et al. 2010 described that iron
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Int. J. Environ. Sci. Technol.
(b) Normal Plot of Residuals
99
95
Normal % Probability
90
80
70
50
30
20
10
2 3 -3 -2 -1 0 1 2
Residuals
ions reduced COD value by increasing the concentration of
iron by 0.33 mM where COD removal reached to 43 from
19%.
Color removal efficiencies were higher in the range of
500–600 mg/L with values of 71.7 and 80.1% and then
decreased to 48% at 750 mg/L at hydrogen peroxide dose
of 4400 mg/L as seen in Fig. 5. As the concentration of
iron increases, self-scavenging effect takes place at a faster
rate than the formation of hydroxyl radical leading to
reduction in COD and decrease in degradation rate of
pollutants as seen in Eq. 9 (Arslan-Alaton et al. 2009).
Fe2þ þ HO ! Feþ3 þ HO ð9Þ
Effect of hydrogen peroxide concentration on COD
and color removal efficiency
As seen in Fig. 4, COD removal efficiencies increased up
to 62% at hydrogen peroxide dose of 4400–6600 mg/L and
then decreased to 56.9% at dose of 8800 mg/L while color
removal efficiencies were higher up to with value of 71% at
dose of 7700 mg/L and decreased to 68% at dose of
8800 mg/L with constant iron dose value of 450 mg/L.
Degradation rate of organic compounds increases with
increased dose of hydrogen peroxide but up to a certain
value until a critical H2O2 concentration is reached.
However, when a concentration higher than critical con-
centration is used, the degradation was condensed due to
scavenging effect as seen in Eqs. 10, 11 and 12 (Hsueh
et al. 2005, Lodha and Chaudhari 2007). From Eq. 10 it
can be conferred that due to the production of peroxyl
radial as well as the scavenging effect of hydrogen
Int. J. Environ. Sci. Technol.

COD removal (%)

8800
50

90

B: Hydrogen Peroxide Dose (mg/L)

7700
80

70
COD removal (%)

6600 5 60
60 70
70

50
80

40 5500
60

450 50
510
4400
570 4400
5500
6600 630 450 510 570 630 690 750
A: Iron Dosage (mg/L)
7700 690 A: Iron Dosage (mg/L)
B: Hydrogen Peroxide Dose (mg/L) 8800 750

Fig. 3 Response surface and contour plots for the effect of iron and hydrogen peroxide concentration on COD removal

Decolorisation (%)
8800
50

90
B: Hydrogen Peroxide Dose (mg/L)

80 7700
Decolorisation (%)

70

6600 5 70 60
60 70

50

40 5500

750 60

690 80 50
8800 630 4400
7700 450 510 570 630 690 750
570
6600 A: Iron Dosage (mg/L)
5500 510 A: Iron Dosage (mg/L)
B: Hydrogen Peroxide Dose (mg/L) 4400 450

Fig. 4 Response surface and contour plots for the effect of iron and hydrogen peroxide concentration on color removal

peroxide, the removal efficiency of COD and color HO  þ HO ! H2 O2 ð12Þ

decreases. The unused quantity of H2O2 also leads to
higher values of COD and might be the possible reason for Also, at higher dosages of H2O2, the deactivation of
more COD values and lesser removal of COD at higher Fe2? takes place which allows the formation of brownish
concentration of H2O2. yellow precipitates and thereby increasing the color of the
wastewater after the critical concentration. Additionally, it
HO  þH2 O2 ! HO2  þH2 O ð10Þ was found that the ratio for influent COD and hydrogen
HO2  þ HO ! O2 þ H2 O ð11Þ peroxide concentration varied in the range of 0.44–0.89,
where it was concluded that maximum removal for COD

123
 Int. J. Environ. Sci. Technol.

and color was obtained at a ratio of 0.65–0.7 and then it
decreased as the concentration of hydrogen peroxide was
not enough for breaking up of recalcitrant dye molecules.
The ratio of hydrogen peroxide concentration to iron
dose was seen in the range of 9.8–11.8 where it was found
that as the ratio increased, the removal was seen in an
ascending manner and then it decreased after a ratio of 11
which concluded that as the ratio increased more peroxyl
radical was produced leading to degradation of organic
molecules but after the critical concentration of hydrogen
peroxide was reached, the removal was lowered.
According to Mansoorian et al. (2014), the COD
removal efficiency increased at H2O2 concentration of
2–5 mM, and then the efficiency decreased after the con-
centration was more than 5 mM. Also, Zhang et al. (2005)
observed that efficiency of hydrogen peroxide for removal
of organic materials in the leachate decreased with the
increase in Fenton reagent dose.
Effect of pH on COD and color removal efficiency
for the decolorization of dyes. Meric et al. (2004) depicted
more than 99% color removal in the pH range of 3–3.5.
Previous studies show that more hydroxyl radicals are
generated in acidic range and this might be the possible
reason of decolorization and COD removal. Under highly
alkaline conditions, the precipitation of Fe(OH)3 occurs;
therefore, the concentration of Fe?3 ions decreases in
wastewater. Also, in alkaline conditions hydrogen peroxide
is less stable, and therefore, lesser is the production of
hydroxyl radicals which leads to the decrement in effi-
ciency of process for color and COD removal (Rodrigues
et al. 2009). At pH below 3, hydrogen peroxide will also
take a proton to form oxonium ion (H3O2)? which pro-
duces more stable hydrogen peroxide and lower its reac-
tivity with ferrous ions (Kavitha and Palanivelu 2005;
Kwon et al. 1999). Under such conditions when pH is \ 3,
reduction in the formation of hydroxyl radicals is due to
decrease in soluble amount of Fe?3 that is in equilibrium
with other iron species (Fe (OH)2) and Fe (OH)?2 (Lucas
and Peres 2006).

As seen in Figs. 5 and 6, maximum COD and color Perturbation plots

removal were obtained in the range of 3–3.2. Efficiency for
COD removal increased from 47.5 to 61% at pH from 2.5
to 3 and then decreased to 56% at pH 3.5 at iron dose of
450 mg/L. Color removal efficiency increased from 58 to
68% at pH of 2.5–3 and then decreased to 61% at pH of
3.5. The values obtained are sustained by previous studies
as Lucas and Peres (2006) observed an optimum pH of 3
Perturbation plots shows the effect when all factors at opti-
mal experimental conditions in the design space are com-
pared at center point. When the factor curvature is sharper,
this factor is more important for the response (Saldańa-
Robles et al. 2014). Figure 7 shows the perturbation plots for
COD and color removal. Here, in the plots, A represents iron

COD removal (%)

3.5
60
50

90
3.3

80
COD removal (%)

70 3.1
C: pH

5 60
60

2.9
50
80

40
2.7 60

450 50
510 50
2.5 70
570 2.5
2.7
2.9 630 450 510 570 630 690 750
3.1
3.3 690 A: Iron Dosage (mg/L) A: Iron Dosage (mg/L)
C: pH 3.5 750

Fig. 5 Response surface and contour plots for the effect of pH on COD removal

123
Int. J. Environ. Sci. Technol.

Decolorisation (%)
3.5

90

3.3
80
Decolorisation (%)

70
3.1
60

C: pH
70 5 70 60
80 80
50
2.9
40

2.7
3.5 50
3.3
750
3.1 60
690 2.5
2.9 630
450 510 570 630 690 750
C: pH 2.7
570
510 A: Iron Dosage (mg/L) A: Iron Dosage (mg/L)
2.5 450

Fig. 6 Response surface and contour plots for the effect of pH on color removal

Perturbation Perturbation
90 90
B
C
C
80 80 B
B
Decolorisation (%)
COD removal (%)

C
B C
70 70
A
A
60 60

A
A
50 50

40 40

-1.000 -0.500 0.000 0.500 1.000 -1.000 -0.500 0.000 0.500 1.000
Deviation from Reference Point (Coded Units) Deviation from Reference Point (Coded Units)

Fig. 7 Perturbation plots for COD and color removal

dose, B represents hydrogen peroxide dose, and C represents Optimization of Fenton treated simulated textile
pH. It can be seen from the graph that factor A is having the wastewater for COD and color removal
steepest slope as compared to factor B and C having rela-
tively flat slopes for both COD and color removal. A steeper In case of assorted responses, RSM appoints set of specific
slope is showing that the response is more sensitive to that working conditions that functions in maximizing all
factor as compared to the other two factors taken for con- responses or at least keeps them in the desired ranges
sideration. The plots generated are nothing but ‘‘one factor at (Myers and Montgomery 2002). In this study, the chosen
a time’’ experimentation where only one factor is varied objectives in terms of color and COD removal efficiencies
keeping others constant. were represented as ‘‘maximize’’ to achieve maximum

123

treatment while the process variables Fe2? and H2O2
concentrations were selected to be ‘‘minimize’’ considering
operating costs while pH variable was chosen with a con-
dition of ‘‘maximize’’ with reference to less usage of
chemicals. Subsequently, optimum working conditions and
respective percent removal efficiencies were retrieved. The
optimum values obtained with the application of these
confined conditions were: Fe2? dose—550 mg/L, H2O2
dose—5538 mg/L, pH—3.3 with COD and color removal
of 73.86 and 81.35%.
An additional study was conducted applying the optimal
conditions to certify the agreement of results achieved from
models. It was found that the values obtained were in close
agreement with the model values, i.e., COD removal
-74.2% and color removal -80.4% with standard devia-
tion of % ±1.23% and ±2.48 at an interval of ±5%. It can
be known that COD and color removal response surface
plots showed clear peaks which proved that the optimal
conditions of Fe2? dose, H2O2 dose and pH were within the
design boundary. High R2 values of the models indicated
that RSM approach was suitable and precise for predicting
Fenton parameters which was conferred well with the
experimental results.
Conclusion
In this work, simulated textile wastewater was treated by
Fenton method and optimization of operational parameters
was studied. Box–Behnken design and response surface
methodology were exercised to assess the independent and
interactive effects of the parameters involved in study. The
quadratic models generated showed immense significance
with high values of R2 showing that the predicted values
matched the experimental ones quite fairly. Dosage of iron
was the most significant factor as obtained from perturba-
tion plots for both COD and color removal. Also, to check
the normality assumption, plot of residuals were found in a
straight manner showing satisfactory results for both mod-
els. Response surface and contour plots showed the effects
of operational parameters in a logical manner. Based on the
model prediction, the optimum conditions were obtained as
Fe2? dose—550 mg/L, H2O2 dose—5538 mg/L, pH—3.3
with COD and color removal efficiencies of 73.86 and
81.35%. Therefore, it was found relevant to use Fenton
treatment for simulated textile wastewater. Viewing the
results, Fenton treatment will prove as a reasonable method
as a pretreatment to textile wastewater where direct bio-
logical oxidation is not possible due to the presence of
recalcitrant organic molecules of dyes.
123
Int. J. Environ. Sci. Technol.
Lastly, a considerable attention can be given upon
coupling of Fenton process with an optimized dosage with
biological aerobic/anaerobic treatment which can lead to
environmental friendly and feasible solution to such type of
textile wastewaters.
Acknowledgements First of all, I would like to thank God, without
his blessings my work would not have been completed. I am
immensely grateful and thankful to my guide. He not only provided
great support for my work, but was also a constant source of inspi-
ration and encouragement. He arranged all the possible support when
I was in need of it. I heartily thank him for his guidance throughout
my work.
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